Conversion of hydrocarbon oils



20% and 40% of the weight of the cl Patented Nov. 18, 1947 UNITED STATES PATENT. oFFica coNvEnsmN 1:15:20cannon: oILs William 'E. Rouge,

No Drawing.

Spicer and Jerry A. Pierce, La., asslgnors to ment Company, a clinic Baton Standard Oil Developratlon of Delaware Application November 20, 1946. SeriaI No. 711,192

7 Claims. (Cl. 19652) filed August 19, 1943, tion-in-part of our application serial No. 454,402, filed August 11, 1942. The present case is also a continuation-in-part of our case, Serial No. 689,183, filed August 8, 1946.

The invention is directed particularly to the preparation of catalysts produced from natural clays for the conversion of hydrocarbon oils. The

of acid normally used ranges between More recently, it has been found more drastic treatment minum hydroxide with ammonium hydroxide.

as herein employed been initially in our earlier applications, Serial Nos. 454,402

and 689,183, above mentioned. Clays of the char 2 acter described in applications Serial No. 454,402 and Serial No. 689,183 may be treated according to the present invention to produce catalysts.

The modified modified clays tends to reduce the deactivating Example 1 A bentonite clay was initially digested with 0.75 part of sulfuric acid concentration of the acid Example 2 Catalysts prepared as described in Example 1 were first treated in a steam atmosphere at 1050 F. This steam-treated product. when tested under conditions set forth in Example 1, gave a gasoline yield of only 44.5%, thus showing that the steam treatment reduced the activity Example 3 Example 4 The catalyst described in Example 3 was treated in a steam atmosphere for 8 hours at a temperature of 1050 F. and thereafter tested as described in Example 1. The steam-treated product produced a gasoline yield of about 46.5 volume percent during the first two cycles.

From a comparison of Examples 3 and 4 it will be noted that the steam treatment reduced the activity of the catalyst magnesium oxide only 1% the catalyst to which no been added.

The amount of magnesium oxide incorporated into the acid treatment may range from 0.1 to 5% or more by weight on the clay, the preferred amount being between 0.5 and 1.5%.

While magnesium oxide has been-found particularly effective, other alkaline earth metal oxides, such as calcium oxide and barium oxide may also be capable of producing substantially the same result. These various oxides may be incorporated into the pretreated clay by precipitation in any known manner from the soluble salts of the corresponding metals, e. g. by precipitation from the corresponding nitrates, chlorides and sulphates.

We claim:

1. The process for cracking hydrocarbon oils which comprises passing the oil to be cracked in contact with a catalyst formed by treating a bentonite clay with 0.5 to 1.50 parts of 100% sulfuric acid diluted to about 12% concentration by weight per part of clay by weight for a length of time efiective to remove a substantial amount of the alumina content of said clay and thereafter incorporating from 0.1 to 5% magnesia by weight therein and keeping said oil vapors in contact with the clay at the cracking temperature for a period sufficient to convert a substantial portion thereof into lower boiling hydrocarbons.

2. The method of preparing a catalyst for the conversion of hydrocarbon oils which comprises treating a bentonite claywith 0.5 to 1.50 parts of 100% sulfuric acid diluted to about 12% concentration by weight per part of clay by weight for a length of time effective to remove a substantial amount of the alumina content of said clay and thereafter incorporating from 0.1 to 5% magnesia by weight therein,

3. The process for cracking hydrocarbon oils which comprises passing the oil to be cracked in contact with a catalyst formed by treating 9, bentonite clay with 0.5 to 1.50 parts of 100% sulfuric acid diluted to about 12% concentration by weight per part of clay by weight for a length of time effective to remove a substantial amount of the alumina content of said clay and thereafter incorporating from 0.1 to 5% magnesia by weight and also 0.1 to 5% alumina by weight therein and keeping said oil vapors in contact with the clay as compared to 5% for magnesium oxide had containing the added at the cracking temperature for a period sufficient to convert a substantial portion thereof into lower boiling hydrocarbons.

4. The method of preparing a catalyst for the conversion of hydrocarbon oils which comprises treating a bentonite clay with 0.5 to 1.50 parts of sulfuric acid diluted to about 12% concentration by weight per part of clay by weight for a length of time eflectivc to remove a substantial amount of the alumina content of said clay and thereafter incorporating from 0.1 to 5% magnesia by weight and also 0.1 to 5% alumina, by weight therein. 1

5. A catalyst for the conversion of hydrocarbon oils characterized by its stability in the presence of steam at elevated temperatures and prepared by treating a. bentonite clay with 0.5 to 1.50 parts of 100% sulfuric acid diluted to about 12% concentration by weight per part 01! clay by weight for a length of time effective to remove a substantial amount of the alumina content of said clay and thereafter incorporating from 0.1 to 5% magnesia by weight therein.

6. A catalyst for the conversion of hydrocarbon oils characterized by its stability in the presence of steam at elevated temperatures and prepared by treating a bentonite clay with 0.5 to 1.50 parts of 100% sulfuric acid diluted to about 12%concentration by weight per part of clay by weight for a length of time effective to remove a substantial amount of the alumina content of said clay and thereafter incorporating from 0.1 to 5% magesia by Weight and also 0.1to 5% alumina by weight therein.

7. A process for cracking hydrocarbon oils which comprises passing the oil to be cracked in contact with a catalyst formed by treating a bentonite clay with 0.75 part of concentrated sulfuric acid diluted to about 12% concentration by weight per part of clay by weight for a time effective to remove a substantial amount of the alumina of the clay and thereafter incorporating therein about 0.5% magnesia by Weight on the clay and keeping the oil vapors in contact with the treated clay catalyst at the cracking temperature for a time suficient to convert a substantial portion thereof into lower boiling hydrocarbons.

WILLIAM E. SPICER. JERRY A. PIERCE.

REFERENCES CITED UNITED STATES PATENTS Number Name Date 2,320,799 Ruthrufi June 1, 1943 2,078,945 Houdry May 4, 1937 1,837,971 Joseph Dec. 22, 1931 1,926,148 Huber Sept. 12, 1933 2,326,166 Pier et al Aug. 10, 1943 2,141,185 Houdry Dec. 27, 1938 2,288,874 Anderson et al July "I, 1942 2,319,590 Eastman et a1 May 18, 1943 1,784,509 Baylis Dec. 9, 1930 1,397,113 Prutzman Nov. 15, 1921 FOREIGN PATENTS Number Country Date 490,853 Great Britain Aug. 23, 1938 OTHER REFERENCES Dunstan et al., Science of Petroleum, vol. 111, pages 1686-7, published 1938 by Oxford University Press, N. Y. (Copy in Division 31.) 

